CN115739120A - Heterojunction photocatalyst integrating full-spectrum response and photothermal effect and preparation and application thereof - Google Patents
Heterojunction photocatalyst integrating full-spectrum response and photothermal effect and preparation and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims abstract description 10
- 229930195725 Mannitol Natural products 0.000 claims abstract description 10
- 239000000594 mannitol Substances 0.000 claims abstract description 10
- 235000010355 mannitol Nutrition 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 4
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- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 3
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- 238000000034 method Methods 0.000 claims description 6
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- 229940036348 bismuth carbonate Drugs 0.000 claims description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 2
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
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- 230000001699 photocatalysis Effects 0.000 description 16
- -1 polytetrafluoroethylene Polymers 0.000 description 10
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- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 description 3
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- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
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- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a preparation method of a heterojunction photocatalyst integrating full-spectrum response and photothermal effect, which comprises the following steps: dissolving a bismuth source in a mannitol solvent, uniformly stirring, adding an aqueous solution containing a chlorine source, and performing hydrothermal reaction, centrifuging, washing and drying on the aqueous solution to obtain a BiOBr precursor; adjusting the proportion of BiOBr and a sulfur source, adding the BiOBr and the sulfur source into deionized water, and uniformly stirring; carrying out secondary hydrothermal reaction on the obtained mixed solution to obtain BiOBr/Bi 2 S 3 The photocatalyst is applied to degrading organic dyes, antibiotics and heavy metal pollutants. The material prepared by the invention has high-efficiency catalytic reduction effect, and has the advantages of high separation efficiency of photon-generated carriers, effective utilization of near infrared light and high catalytic efficiency; the material has simple preparation method, mild reaction condition and low cost, is suitable for large-scale production, and is a novel and efficient material for photocatalytic degradation of Cr (VI).
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a heterojunction photocatalyst integrating full-spectrum response and photothermal effect, and preparation and application thereof.
Background
With the acceleration of industrialization and urbanization processes, the unreasonable discharge of industrial wastewater and domestic sewage can cause serious pollution to water bodies, so that various pollutants which are difficult to degrade in water are accumulated, and great influence is caused to the environment and human health. Semiconductor photocatalysis is a high-efficiency utilization technology of clean energy, and is considered to be one of effective means for solving the current environmental pollution problem.
BiOBr as a layered semiconductor has better performance in the aspects of optics, electrics, magnetism, photocatalysis and the like, thereby attracting wide attention and research. However, the photocatalytic efficiency is limited due to the narrow spectral response range and the easy recombination of the photo-generated electron-hole pairs. Therefore, it remains a great interest and challenge to develop a BiOBr-based composite material with high photogenerated carrier separation efficiency, broad spectral response, and low cost.
In recent years, the construction of heterojunctions has become a hot research point for improving the photocatalytic performance of semiconductor materials. Research shows that the heterojunction can improve the efficiency of electron separation and carrier transfer and reduce the recombination probability of electron-hole pairs. However, the narrow photoresponse range is still one of the key factors that restrict the photocatalytic efficiency.
Bismuth sulfide (Bi) 2 S 3 ) A narrow bandgap semiconductor has a light response capability over the entire visible light range. These characteristics are such that Bi 2 S 3 Becoming sensitizers for many wide band gap semiconductors. For example, with cadmium sulfide, bi 4 Ti 3 O 12 、BiFeO 3 Etc. It has been found that this combination is beneficial in improving visible light absorption and photogenerated carrier separation. In particular, the two species in the heterogeneous structure have the same elements, which is advantageous for building a close contact interface. In recent years, biOBr/Bi 2 S 3 Heterojunctions are constructed for the degradation of organic pollutants, organophosphorus pesticide detection, and pharmaceuticals. However, with respect to in situ synthesis of BiOBr/Bi 2 S 3 The research on the photocatalytic reduction of Cr (VI) by the heterojunction is less, and Bi is not fully utilized 2 S 3 Excellent near infrared absorption capacity and photo-thermal characteristics, resulting in limited enhancement of photocatalytic activity. Therefore, a new method was developed for in situ synthesis of BiOBr/Bi 2 S 3 The heterojunction photocatalyst has better research significance and research value for developing Bi series photocatalytic materials and application thereof.
Therefore, in order to solve the above problems, a heterojunction photocatalyst integrating a full spectrum response and a photothermal effect, and preparation and application thereof are provided.
Disclosure of Invention
In order to solve the technical problems, the invention designs the heterojunction photocatalyst integrating the full-spectrum response and the photothermal effect, and the preparation and the application thereof.
In order to achieve the technical effects, the invention is realized by the following technical scheme: a preparation method of a heterojunction photocatalyst integrating full-spectrum response and photothermal effect is characterized by comprising the following steps:
step1, dissolving a bismuth source in a mannitol solvent, uniformly stirring, adding an aqueous solution containing a chlorine source, and performing hydrothermal reaction on the obtained aqueous solution, centrifuging, washing and drying to obtain a BiOBr precursor;
step2, adjusting the proportion of BiOBr and a sulfur source, adding the mixture into deionized water, and uniformly stirring;
and Step3, carrying out secondary hydrothermal reaction on the mixed solution obtained in Step2, wherein the hydrothermal reaction temperature is 120-220 ℃, and the hydrothermal reaction time is 6-36 h, thus obtaining the catalyst.
Further, the mass ratio of the bismuth source to the mannitol solution in Step1 is 0.1-3g;
the bismuth source is one or more of bismuth nitrate pentahydrate, bismuth carbonate, bismuth phosphate, bismuth sulfate and bismuth trioxide.
Further, the chlorine source in Step1 is one or more of sodium chloride, potassium chloride, calcium chloride, ammonium chloride and hexadecyl trimethyl ammonium chloride;
the concentration of the aqueous solution containing the chlorine source is 0.5-5M.
Further, the sulfur source in Step2 is one or more of sodium sulfide, sodium thiosulfate, thiourea and ammonium sulfide;
the concentration of the aqueous solution containing the sulfur source is 0.5-5M.
Furthermore, the molar ratio of the bromine in the bromine source to the bismuth in the bismuth source is 0.5-5:1;
the molar ratio of the sulfur element in the sulfur source to the bismuth element in the bismuth oxybromide is 0.05-5:1.
Another object of the present invention is to provide a heterojunction photocatalyst integrating a full-spectrum response and a photothermal effect, wherein the chemical formula is: biOBr/Bi 2 S 3 。
Furthermore, the photocatalyst is applied to degradation of organic dyes, antibiotics and heavy metal pollutants.
The invention has the beneficial effects that:
BiOBr/Bi prepared by the invention 2 S 3 Heterojunction photocatalystThe catalyst has high-efficiency catalytic reduction effect on Cr (VI), and has the advantages of high separation efficiency of photon-generated carriers, effective utilization of near infrared light and high catalytic efficiency; meanwhile, the material preparation method is simple, the reaction condition is mild, the cost is low, the material is suitable for large-scale production, and the material is a novel and efficient material for photocatalytic degradation of Cr (VI).
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows BiOBr/Bi prepared in examples 1 to 4 and comparative examples 1 and 2 2 S 3 An X-ray diffraction pattern of the heterojunction photocatalytic material;
FIG. 2 shows BiOBr/Bi prepared in examples 1-4 and comparative examples 1 and 2 2 S 3 An ultraviolet-visible-infrared absorption spectrum of the heterojunction photocatalytic material;
FIG. 3 shows BiOBr/Bi prepared in examples 1-4 and comparative examples 1 and 2 2 S 3 A performance curve diagram of the full spectrum photocatalytic degradation Cr (VI) of the heterojunction photocatalytic material;
FIG. 4 shows BiOBr/Bi prepared in examples 1-4 and comparative examples 1 and 2 2 S 3 A performance curve diagram of near infrared photocatalytic degradation Cr (VI) of the heterojunction photocatalytic material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Integrating full-spectrum response and photothermal effectBiOBr/Bi 2 S 3 The in-situ preparation method of the Z-type heterojunction composite photocatalyst comprises the following steps:
(1) Adding 2-5mol of bismuth nitrate pentahydrate into 30mL of mannitol aqueous solution (0.1M), stirring until the solution is transparent, adding 0.8-2mL of 2.5M potassium bromide solution, and fully stirring to obtain a mixed solution. And transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is finished to obtain a precipitate.
(2) And (2) centrifugally washing the precipitate obtained in the step (1) by respectively using ionized water and ethanol, and drying at 70 ℃ to obtain the BiOBr precursor.
(3) Mixing BiOBr with Na 2 S 2 O 3 According to the mass amount 1:1 is added into 30ml deionized water, is fully stirred and then is transferred into a polytetrafluoroethylene reaction kettle, carries out hydrothermal reaction for 6 hours at 180 ℃, and naturally cools to room temperature after the reaction is finished to obtain the precipitate.
(4) Centrifugally washing the precipitate obtained in the step (3) by respectively using ionized water and ethanol, and drying at 70 ℃ to obtain BiOBr/Bi 2 S 3 A heterojunction photocatalyst, labeled B-2S.
Example 2
BiOBr/Bi integrating full-spectrum response and photothermal effect 2 S 3 The in-situ preparation method of the Z-type heterojunction composite photocatalyst comprises the following steps:
(1) Adding 2-5mol of bismuth sulfide into 30mL of mannitol aqueous solution (0.1M), stirring until the solution is transparent, adding 0.8-2mL of 2.5M sodium bromide solution, and fully stirring to obtain a mixed solution. And transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is finished to obtain a precipitate.
(2) And (2) centrifugally washing the precipitate obtained in the step (1) by respectively using ionized water and ethanol, and drying at 70 ℃ to obtain the BiOBr precursor.
(3) Mixing BiOBr with Na 2 S 2 O 3 According to the mass 1:0.5 is added into 30ml of deionized water, and the mixture is transferred to polytetrafluoroethylene after being fully stirredAnd (3) carrying out hydrothermal reaction for 6 hours at 180 ℃ in an alkene reaction kettle, and naturally cooling to room temperature after the reaction is finished to obtain a precipitate.
(4) Centrifugally washing the precipitate obtained in the step (3) by respectively using ionized water and ethanol, and drying at 70 ℃ to obtain BiOBr/Bi 2 S 3 A heterojunction photocatalyst, labeled B-1S.
Example 3
BiOBr/Bi integrating full-spectrum response and photothermal effect 2 S 3 The in-situ preparation method of the Z-type heterojunction composite photocatalyst comprises the following steps:
(1) Adding 2-5mol of bismuth nitrate pentahydrate into 30mL of mannitol aqueous solution (0.1M), stirring until the solution is transparent, adding 0.8-2mL of 2.5M sodium bromide solution, and fully stirring to obtain a mixed solution. And transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is finished to obtain a precipitate.
(2) And (2) centrifugally washing the precipitate obtained in the step (1) by respectively using ionized water and ethanol, and drying at 70 ℃ to obtain the BiOBr precursor.
(3) Mixing BiOBr with Na 2 S 2 O 3 According to the mass 1:1.5 is added into 30ml deionized water, is transferred into a polytetrafluoroethylene reaction kettle after being fully stirred, carries out hydrothermal reaction for 6 hours at 180 ℃, and is naturally cooled to room temperature after the reaction is finished, thus obtaining the precipitate.
(4) Centrifugally washing the precipitate obtained in the step (3) by respectively using ionized water and ethanol, and drying at 70 ℃ to obtain BiOBr/Bi 2 S 3 A heterojunction photocatalyst, labeled B-3S.
Example 4
BiOBr/Bi integrating full-spectrum response and photothermal effect 2 S 3 The in-situ preparation method and the application of the Z-type heterojunction composite photocatalyst comprise the following steps:
(1) Adding 2-5mol of bismuth sulfide into 30mL of mannitol aqueous solution (0.1M), stirring until the solution is transparent, adding 0.8-2mL of 2.5M potassium bromide solution, and fully stirring to obtain a mixed solution. And transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is finished to obtain a precipitate.
(2) And (2) centrifugally washing the precipitate obtained in the step (1) by respectively using ionized water and ethanol, and drying at 70 ℃ to obtain the BiOBr precursor.
(3) Mixing BiOBr with Na 2 S 2 O 3 According to the mass 1:0.25 is added into 30ml deionized water, the mixture is transferred into a polytetrafluoroethylene reaction kettle after being fully stirred, the hydrothermal reaction is carried out for 6 hours at 180 ℃, and the mixture is naturally cooled to room temperature after the reaction is finished, thus obtaining the precipitate.
(4) Centrifugally washing the precipitate obtained in the step (3) by respectively using ionized water and ethanol, and drying at 70 ℃ to obtain BiOBr/Bi 2 S 3 Heterojunction photocatalyst, labeled B-0.5S.
Comparative example 1
A preparation method and application of a BiOBr photocatalyst comprise the following steps:
(1) Adding 2-5mol of bismuth nitrate pentahydrate into 30mL of mannitol aqueous solution (0.1M), stirring until the solution is transparent, adding 0.8-2mL of 2.5M potassium bromide solution, and fully stirring to obtain a mixed solution. And transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is finished to obtain a precipitate.
(2) And (2) centrifugally washing the precipitate obtained in the step (1) by respectively using ionized water and ethanol, and drying at 70 ℃ to obtain the BiOBr precursor.
Comparative example 2
Bi 2 S 3 The preparation method and the application of the photocatalyst comprise the following steps:
(1) Adding 2-5mol of bismuth nitrate into 30mL of deionized water, stirring uniformly, and adding 2-5mol of Na 2 S 2 O 3 And adding 0.2-0.5g of urea into the obtained mixed solution after uniformly stirring. And transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is finished to obtain a precipitate.
(2) Centrifugally washing the precipitate obtained in the step (1) by respectively using ionized water and ethanol, and drying at 70 ℃ to obtain Bi 2 S 3 A photocatalyst.
Photocatalytic activity test
The photocatalytic activity of the samples on Cr (VI) degradation was evaluated under a 300W xenon lamp (CEL-LAX 500). The reactor used was a custom-made quartz reactor with a volume of 100ml, and 20mg of the sample was added to a potassium dichromate solution (40mL, 10mg/L) and stirred in the dark for 2 hours to ensure absorption-desorption equilibrium. Periodically, 4mL of the reaction mixture were removed. The supernatant was analyzed with a UV-1800 spectrophotometer.
As can be seen from FIG. 1, the photocatalysts prepared in the examples and comparative examples all correspond to the standard BiOBr and Bi 2 S 3 Characteristic peaks, no impurity peaks, indicate high sample preparation purity. As can be seen from FIG. 2, the photocatalytic activities of examples 1-3 were all higher than those of the comparative examples, and the activity of example 1 was the highest, and the removal rate of Cr (VI) within 10min could reach 100%. As can be seen from FIG. 3, the absorption spectra of examples 1-4 are all broadened to the infrared region, and the near-infrared catalysis results of FIG. 4 show that the BiOBr/Bi prepared 2 S 3 The heterojunction photocatalyst can effectively utilize near infrared light.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (7)
1. A preparation method of a heterojunction photocatalyst integrating full-spectrum response and photothermal effect is characterized by comprising the following steps:
step1, dissolving a bismuth source in a mannitol solvent, uniformly stirring, adding an aqueous solution containing a chlorine source, and performing hydrothermal reaction on the obtained aqueous solution, centrifuging, washing and drying to obtain a BiOBr precursor;
step2, adjusting the proportion of BiOBr and a sulfur source, adding the mixture into deionized water, and uniformly stirring;
and Step3, carrying out secondary hydrothermal reaction on the mixed solution obtained in Step2, wherein the hydrothermal reaction temperature is 120-220 ℃, and the hydrothermal reaction time is 6-36 hours.
2. The method for preparing a heterojunction photocatalyst integrating the full-spectrum response and the photothermal effect as claimed in claim 1, wherein: the mass ratio of the bismuth source to the mannitol solution in Step1 is 0.1-3g;
the bismuth source is one or more of bismuth nitrate pentahydrate, bismuth carbonate, bismuth phosphate, bismuth sulfate and bismuth trioxide.
3. The method for preparing a heterojunction photocatalyst integrating the full-spectrum response and the photothermal effect as claimed in claim 1, wherein: the chlorine source in Step1 is one or more of sodium chloride, potassium chloride, calcium chloride, ammonium chloride and hexadecyl trimethyl ammonium chloride;
the concentration of the water solution containing the chlorine source is 0.5-5M.
4. The method for preparing a heterojunction photocatalyst integrating the full-spectrum response and the photothermal effect as claimed in claim 1, wherein: the sulfur source in Step2 is one or more of sodium sulfide, sodium thiosulfate, thiourea and ammonium sulfide;
the concentration of the aqueous solution containing the sulfur source is 0.5-5M.
5. The method for preparing a heterojunction photocatalyst integrating the full-spectrum response and the photothermal effect as claimed in claim 1, wherein: the molar ratio of the bromine in the bromine source to the bismuth in the bismuth source is 0.5-5:1;
the molar ratio of the sulfur element in the sulfur source to the bismuth element in the bismuth oxybromide is 0.05-5:1.
6. A heterojunction photocatalyst integrating a full-spectrum response and a photothermal effect is characterized by having a chemical formula: biOBr/Bi 2 S 3 。
7. The heterojunction photocatalyst integrating the full-spectrum response and the photothermal effect as claimed in claim 6, wherein the heterojunction photocatalyst is applied to the degradation of organic dyes, antibiotics and heavy metal pollutants as the photocatalyst.
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